CN108641122B - A kind of palygorskite Quito functional polymer material auxiliary agent and preparation method thereof - Google Patents
A kind of palygorskite Quito functional polymer material auxiliary agent and preparation method thereof Download PDFInfo
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- CN108641122B CN108641122B CN201810349919.XA CN201810349919A CN108641122B CN 108641122 B CN108641122 B CN 108641122B CN 201810349919 A CN201810349919 A CN 201810349919A CN 108641122 B CN108641122 B CN 108641122B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
A kind of palygorskite Quito functional polymer material auxiliary agent of the present invention and preparation method thereof, is to crush palygorskite, and coupling agent is added, and stirring at normal temperature processing obtains the modified palygorskite in surface, and drying simultaneously crushes again；Then it disperses the modified palygorskite in surface in ethyl acetate, sequentially adds compound 1- propylphosphonic anhydride, compound 5- aminotetrazole first stirs a period of time after ultrasound；Most through pneumatic conveying drying and recycle ethyl acetate solvent afterwards, it is dry after powder product it is ground to get palygorskite Quito functional polymer auxiliary agent.Experiment shows, palygorskite Quito prepared by the present invention function additive has excellent comprehensive performance, the thermal stability of material can comprehensively be improved, crosslinking degree, anti-flammability, tensile strength and impact strength, and the toxicity after smoke density and burning can be reduced, it is a kind of more satisfactory high molecular material multifunctional assistant, there is good prospect in the modified field of polymer composite.
Description
Technical field
The present invention relates to a kind of high molecular material auxiliary agent more particularly to a kind of palygorskite based high molecular material additive and
Preparation method belongs to composite material technical field of function materials.
Background technique
High molecular synthetic material, such as polypropylene, polyethylene, polystyrene, nylon, rubber are goed deep into every profession and trade
It is widely applied.But demand of each industry to high molecular material is different, this also determines a kind of high molecular synthetic material not
May be it is omnipotent, need in application process the particularity such as the material according to product, performance require be adjusted.
High polymer material chemical auxiliary agent refers to improve the high molecular materials processing performances such as plastics, rubber, improve physical machine
Tool performance, enhancing function assign certain distinctive application performance of high molecular material and are added in target material Polymer Systems
Various auxiliary substances, usually also known as chemical addition agent, polymeric additive (auxiliary agent), high molecular material additive (auxiliary agent) etc..
Plastic additive, resin raw material and plastic processing machinery together constitute the three basic elements of plastic processing.In this plastic additive
What is inventionbroadly referred to is exactly high molecular material function additive.There are many type of high molecular synthetic material auxiliary agent, as plasticizer, heat are steady
Determine agent, light stabilizer, antioxidant, crosslinking agent, foaming agent, fire retardant, lubricant, antistatic auxiliary, antifoggant, curing agent,
Vulcanizing agent, anti-aging agent, filler etc..The effect of these auxiliary agents is: make high molecular material during processing and use more
Stablize, processing performance is more excellent, and mechanical property can increase or keep, other physical properties can satisfy to be wanted using field
It asks.Impact modifier is used to be modified the auxiliary agent of certain thermal plastic high polymer impact properties, and low impact property is certain thermoplasticity polymerizations
The shortcomings that object, such as the notch and unnotched impact strength of PVC, PP, PS, PLA, PET are all very low, and especially low-temperature impact is strong
Degree.Crosslinking agent is a kind of heated or energy excitation release free radical activation macromolecular chain, make to occur between them chemical reaction and
The auxiliary agent being cross-linked with each other, linear thermoplastic resin pass through the available tridimensional network of cross-linking reaction, this structure
The not high disadvantage of high molecular poor heat resistance, mechanical strength can be improved.Multi-functional reinforcing agent, which refers to, is added reinforcing agent in polymer,
Its mechanical property (tensile strength and elongation at break) can be increased substantially, dimensional stability and heat distortion temperature can be preferable
Its toughness of holding and fatigue durability.Fire retardant refers to the function additive is added in high molecular synthetic material after, can be apparent
Improve the flame resistant ability of material.Smoke suppressant refers to reduce smoke density of high molecular synthetic material when burning.It is attenuated agent
It refers to reduce noxious material such as carbon monoxide, two that high molecular material discharges after use process, degradation process or burning
Carbonoxide etc..In all high molecular synthetic materials, stabilizing additive can inhibit or delay polymer storage, transport,
Degradation with aging in processing and application extends the auxiliary agent of product service life.
The one multifunction of high molecular synthetic material auxiliary agent and the high-effect chemical conversion of single dose single function are modern auxiliary agent research and development
Trend.In addition, auxiliary agent is also in use one of the emphasis considered to the pollution of environment and secondary disaster.Therefore green ring
It protects, efficient, multi-functional, less toxic, low pollution function additive is all industries and the target that scientific research personnel pursues.
Summary of the invention
The object of the present invention is to provide it is a kind of collect stabilizer, crosslinking agent, fire retardant, smoke suppressant, attenuation agent and reinforcing agent in
The preparation method of the multifunctional macromolecule additive synthesis of one.
One, the preparation of multifunctional assistant
The preparation of multifunctional macromolecule material additive of the present invention: being crushed to 4000 mesh or more for palygorskite, is added even
Join agent and stir 1 ~ 5 hour, obtain the modified palygorskite in surface, drying is simultaneously crushed to 4000 mesh or more again；Again by table
The modified palygorskite in face is scattered in ethyl acetate, sequentially adds compound 1- propylphosphonic anhydride, compound 5- amino four
Nitrogen azoles, first 30 ~ 120 min of ultrasound, are stirred for 1 ~ 3 hour；Then through pneumatic conveying drying and ethyl acetate solvent is recycled；After drying
Powder product is ground to get multifunctional macromolecule additive synthesis.
Coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, Organic Chromium complex coupling agent, phosphorus
Acid esters, borate, stannic acid ester, zirconate, zirconium aluminate；The additional amount of coupling agent is the 1% ~ 15% of palygorskite quality.
The additional amount of compound 1- propylphosphonic anhydride (CAS:68957-94-8) be palygorskite butt quality 5% ~
40%；
The additional amount of compound 5- aminotetrazole (CAS:4418-61-5) be palygorskite butt quality 8% ~
60%。
Grinding is ground 0.2 ~ 0.5 hour at (1800 ~ 2500 revs/min) of high speed in the ball mill,
Two, the performance of multifunctional assistant
It is acted on to verify the function additive to the performance of high molecular synthetic material, the present invention has selected representative
High molecular material: polypropylene, low density polyethylene (LDPE) and polyvinyl chloride are matrix, have studied the performance of the function additive.Function helps
The additive amount of agent is the 3% of matrix.Specific test result is shown in Table 1(and adds all property of composite material after function additive of the present invention
Can change is the result being compared relative to pure substrate performance):
In order to illustrate the effect of addition 1- propylphosphonic anhydride and 5- aminotetrazole material, using low density polyethylene (LDPE) as matrix
Material, and performance comparison is carried out by comparative test: in comparative test 1, palygorskite quality 40% is only added in function additive
1- propylphosphonic anhydride, total addition level remains as 3% to comparing function auxiliary agent 1 in the base.Palygorskite is only added in comparative test 2
The 5- aminotetrazole of clay quality 60%, total addition level remains as 3% to comparing function auxiliary agent 2 in the base.In comparative test 3 only
Coupling agent modified palygorskite is added, total addition level remains as 3% to comparing function auxiliary agent 3 in the base.It the results are shown in Table 2:
By comparing above as can be seen that multifunctional assistant prepared by the present invention has excellent comprehensive performance, energy is comprehensively
Raising material thermal stability, crosslinking degree, anti-flammability, tensile strength and impact strength；After reducing smoke density and burning
Toxicity.1- propylphosphonic anhydride and 5- aminotetrazole is added can improve the anti-flammability of material well, reduce composite material
Smoke density.The increase of palygorskite content helps to improve the degree of cross linking, reduces carbon monoxide poison gas content, improves the power of material
Learn performance.
Currently used inorganic environment-friendly fire retardant is magnesium hydroxide and aluminium hydroxide, but both materials will reach fire-retardant
Effect, the additive amount in high molecular material generally will be more than 35%, although the fire-retardant property of composite material is improved, to compound
The mechanical property destruction of material is very serious, and some special trades is caused not to be available, such as military project, space flight and nuclear industry etc..For
The synergistic ability of multifunctional material auxiliary agent in the present invention is investigated, relevant experiment has also been made in we.The study found that with polypropylene
For matrix, the oxygen index (OI) of composite material could be made to reach 28 in the commercially available aluminium hydroxide fire retardant of addition 42%, become fire-retardant material
Material.When we add 3% function additive of the present invention in polypropylene, when so that PP composite material oxygen index (OI) reaching 28,
It only needs to add magnesium hydroxide or aluminium hydroxide fire retardant 20% ~ 25% almost can reduce nothing as can be seen from the comparison result
Machine additive capacity half, bring advantage are that the mechanical property of composite material improves a lot.Polypropylene/42% magnesium hydroxide
The tensile strength average value of composite material is lower than 13MPa, and impact strength is lower than 3.5kJ/m2, and polypropylene/20% magnesium hydroxide/
The tensile strength of 3% aid composite of the present invention is averagely higher than 28.5MPa, and impact strength is averagely higher than 3.7 kJ/m2, thus
It can be seen that function additive of the present invention has excellent synergistic effect.
Specific embodiment
The preparation of synthesis of polymer material auxiliary agent of the present invention, performance are described further below by specific embodiment.
Embodiment 1
Palygorskite is crushed to 4000 mesh or more, the silane coupling agent of its quality 1 ~ 15%, and high-speed stirred is added
Processing 1 hour, obtains modified surface palygorskite, and drying is simultaneously crushed to 4000 mesh or more again；
The palygorskite for taking a certain amount of surface modified, is distributed in ethyl acetate solvent, makes its mass concentration 60%；
It is subsequently added into the compound 1- propylphosphonic anhydride (CAS:68957-94-8) of palygorskite butt quality 40%, palygorskite
The compound 5- aminotetrazole (CAS:4418-61-5) of butt quality 60%, first 30 ~ 120 min of ultrasonic disperse, then machinery stir
It mixes 1 hour；Then it pneumatic conveying drying and recycles ethyl acetate solvent (recycling), obtains powder product；Finally by powder product
High speed grinding 0.5 hour is in the ball mill to get arriving multifunctional macromolecule synthetic material auxiliary agent.
The auxiliary agent is used for the preparation of low-density polyethylene composite material, when the additive amount of auxiliary agent is the 3% of matrix, institute
The performance indicator for obtaining low-density polyethylene composite material is as follows:
Embodiment 2
Palygorskite is crushed to 4000 mesh or more, the silane coupling agent of its quality 1 ~ 15%, and high-speed stirred is added
Processing 1 hour, obtains modified surface palygorskite, and drying is simultaneously crushed to 4000 mesh or more again；
The palygorskite for taking a certain amount of surface modified, is distributed in ethyl acetate solvent, makes its mass concentration 60%；
It is subsequently added into the compound 1- propylphosphonic anhydride (CAS:68957-94-8) of palygorskite butt quality 50%, palygorskite
The compound 5- aminotetrazole (CAS:4418-61-5) of butt quality 80%, first 30 ~ 120min of ultrasonic disperse, then mechanical stirring
3 hours；Then it pneumatic conveying drying and recycles ethyl acetate solvent (recycling), obtains powder product；Finally powder product is existed
Ball mill high speed grinds 0.2 hour to get multifunctional macromolecule synthetic material auxiliary agent is arrived.
The auxiliary agent is used for the preparation of low-density polyethylene composite material, when the additive amount of auxiliary agent is the 3% of matrix, institute
The performance indicator for obtaining low-density polyethylene composite material is as follows:
Embodiment 3
Palygorskite is crushed to 4000 mesh or more, the silane coupling agent of its quality 1 ~ 15%, and high-speed stirred is added
Processing 1 hour, obtains modified surface palygorskite, and drying is simultaneously crushed to 4000 mesh or more again；
The palygorskite for taking a certain amount of surface modified, is distributed in ethyl acetate solvent, makes its mass concentration 60%；
It is subsequently added into the compound 1- propylphosphonic anhydride (CAS:68957-94-8) of palygorskite butt quality 30%, palygorskite
The compound 5- aminotetrazole (CAS:4418-61-5) of butt quality 30%, first 30 ~ 120min of ultrasonic disperse, then mechanical stirring
2 hours；Then it pneumatic conveying drying and recycles ethyl acetate solvent (recycling), obtains powder product；Finally powder product is existed
Ball mill high speed grinds 0.4 hour to get multifunctional macromolecule synthetic material auxiliary agent is arrived.
The auxiliary agent is used for the preparation of low-density polyethylene composite material, when the additive amount of auxiliary agent is the 3% of matrix, institute
The performance indicator for obtaining low-density polyethylene composite material is as follows:
Claims (7)
1. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent, is that palygorskite is crushed to 4000
More than mesh, coupling agent is added, stirring at normal temperature is handled 1 ~ 5 hour, obtains the modified palygorskite in surface, and drying simultaneously crushes again
To more than 4000 mesh；It again disperses the modified palygorskite in surface in ethyl acetate, sequentially adds compound 1- propyl phosphorus
Acid anhydrides, compound 5- aminotetrazole, first 30 ~ 120min of ultrasound, is stirred for 1 ~ 3 hour；Then through pneumatic conveying drying and second is recycled
Acetoacetic ester solvent, the powder product after drying are ground to get palygorskite Quito functional polymer composites auxiliary agent.
2. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent as described in claim 1, feature exist
In: the coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, organochromium complexes coupling agent, phosphoric acid
Ester, borate, stannic acid ester, zirconate, zirconium aluminate.
3. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent as described in claim 1, feature exist
In: the additional amount of coupling agent is the 1% ~ 15% of palygorskite quality.
4. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent as described in claim 1, feature exist
In: the additional amount of compound 1- propylphosphonic anhydride is the 5% ~ 40% of palygorskite butt quality.
5. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent as described in claim 1, feature exist
In: the additional amount of compound 5- aminotetrazole is the 8% ~ 60% of palygorskite butt quality.
6. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent as described in claim 1, feature exist
In: grinding be high speed grinding 0.2 ~ 0.5 hour in the ball mill.
7. a kind of preparation method of palygorskite Quito functional polymer material auxiliary agent as claimed in claim 6, feature exist
In: the speed of the high speed grinding is 1800 ~ 2500 revs/min.
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| CN110628082B (en) * | 2019-10-17 | 2021-05-18 | 西北师范大学 | Multifunctional additive for high polymer material and preparation method thereof |
| CN113307280B (en) * | 2021-06-23 | 2023-01-06 | 西北师范大学 | Method for normalizing quality of attapulgite product |
| CN115777704B (en) * | 2023-02-08 | 2023-04-28 | 潍坊市种子有限公司 | Drought-resistant seed coating agent and preparation method thereof |
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